WO2007068137A1

WO2007068137A1 - The process for preparing biodiesel

Info

Publication number: WO2007068137A1
Application number: PCT/CN2005/001940
Authority: WO
Inventors: Siu Wai Chiu; Yiu Kwong Wong
Original assignee: The Chinese University Of Hong Kong
Priority date: 2005-11-17
Filing date: 2005-11-17
Publication date: 2007-06-21

Abstract

The present invention discloses a process for preparing biodisel containing high purity fatty acid methyl ester by using the fraction of physically refining deodorizing distillation which is byproduct of vegetable oil as raw material. The process comprises: a) reacting the physically refining deodorizing fraction with methanol at 65-85 at the presence of acid catalysts, b) separating fatty acid methyl ester from the resultant mixture.The present invention also discloses a process for treating physically refining deodorizing fraction, comprising to esterify free fatty acid in the physically refining deodorizing fraction to acquire fatty acid methyl ester, and to extract phytosterols from residue free of fatty acid. The present invention reduces the cost by using byproduct of industy as raw material for preparing biodiesel and phytosterols.

Description

生物柴油的制备方法 Method for preparing biodiesel

技术领域 Technical field

本发明涉及以植物油精炼副产物为原料生产生物柴油的方法，特另 'J 涉及以物理精炼脱臭蒸馏物为原料通过酯化生产生物柴油的方法。背景技术 The invention relates to a method for producing biodiesel by using vegetable oil refining by-product as a raw material, and the special method relates to a method for producing biodiesel by esterification using a physical refining and deodorizing distillate as a raw material. Background technique

由于石油资源日益匮乏，造成全球石油价格的不断上升，因此迫切需要替代的可再生能源。生物柴油正是新开发出的替代能源之一，相比石化柴油它具有众多优点，例如可生物降解、低毒性、无公害、低污染物排放等，有利环境健康。 As oil resources become increasingly scarce and global oil prices continue to rise, there is an urgent need for alternative renewable energy sources. Biodiesel is one of the newly developed alternative energy sources. Compared with petrochemical diesel, it has many advantages, such as biodegradability, low toxicity, pollution-free, low pollutant emissions, etc., which is beneficial to the environment.

生物柴油的主要化学成分是脂肪酸曱酯 (methyl esters of fatty acids, FAMEs)。目前生物柴油生产主要采用植物油为原料，少数包括动物脂肪，例如中国专利申奇第 98811443.7号和美国专利申请第 20040074760号。 The main chemical constituents of biodiesel are methyl esters of fatty acids (FAMEs). At present, biodiesel production mainly uses vegetable oil as a raw material, and a few include animal fats, such as Chinese Patent Shenqi No. 98811443.7 and US Patent Application No. 20040074760.

以植物油为原料生产生物柴油主要是借助化学催化或酶法进行酯交换反应（Hsu等， 2002; Xu等， 2003), 使植物油中的游离脂肪酸 (C₁₄-C₂₂) 和甘油酯反应产生脂肪酸曱酯。酯交换反应后，可用多种物理和化学方法对产物进行提取和精炼，例如皂化、酯化和蒸馏等，参见中国专利申请笫 98811443.7号。 The production of biodiesel from vegetable oil is mainly carried out by chemical catalysis or enzymatic transesterification (Hsu et al., 2002; Xu et al., 2003). The free fatty acids (C ₁₄ -C ₂₂ ) and glycerides in vegetable oil are reacted to produce fatty acids. Oxime ester. After the transesterification reaction, the product can be extracted and refined by various physical and chemical methods, such as saponification, esterification and distillation, see Chinese Patent Application No. 98811443.7.

以植物油制备生物柴油成本高，并且依赖于植物的地域分布、产量多寡和种植成本等等，因而具有生产地区的局限性。 The preparation of biodiesel from vegetable oils is costly and depends on the geographical distribution of the plants, the amount of production and the cost of planting, etc., and thus has limitations in the production area.

最近，国内外有很多专家提出用废食用油或隔油池废物来制备生物柴油以降低生产成本 (Al-Widyan & Al-Shyoukh, 2002; Zhang 等， 2003; Canakci & Ozsezen, 2005) 。但是，这些研究多在实验室阶段，并且没有测验产品能否达到现行生物柴油的标准、工艺是否表现稳定成效和是否有稳定供货渠道等。虽然，我国已有釆用废食用油、餐饮地沟油和植物油厂的油脚为原料生产的生物柴油，如公开号为 CN 02133591.5、 CN 01107895.2、 CN 200510200025.7号的中国专利申请，但产品生物柴油颜色深、表观混浊，需采用脱色方法处理。原料质量不稳定。如此，不但增加成本，而且脂肪酸甲酯损失大、且效果不好。 Recently, many experts at home and abroad have proposed using waste cooking oil or grease trap waste to prepare biodiesel to reduce production costs (Al-Widyan & Al-Shyoukh, 2002; Zhang et al., 2003; Canakci & Ozsezen, 2005). However, these studies are mostly in the laboratory stage, and there is no test whether the products can meet the current biodiesel standards, whether the process is stable and effective, and whether there are stable supply channels. Although China has used biodiesel produced from waste cooking oil, catering waste oil and vegetable oil plant as raw materials, such as Chinese patent application published as CN 02133591.5, CN 01107895.2, CN 200510200025.7, but the product biodiesel color Deep, apparent turbidity, need to be treated by decolorization. The quality of raw materials is unstable. In this way, not only the cost is increased, but also the fatty acid methyl ester loss is large and the effect is not good.

另一种潜在的生物柴油原料是植物油精炼副产物。植物油精炼方法包括化学精炼法及物理精炼法。与化学精炼相比，物理精炼具有油产量多、提炼时间短、设备及运作成本低等诸多优点 (Kellens & Greyt, 2000; Zlich, 2000) , 因此应用越来越广泛。但无论何种精炼方法，均采用蒸熘方法进行脱臭。上述脱臭蒸馏物通常含有：游离脂肪酸、甘油酯、不皂化物Another potential biodiesel feedstock is a by-product of vegetable oil refining. Vegetable oil refining methods include chemical refining and physical refining. Compared with chemical refining, physical refining has many advantages such as oil production, short refining time, low equipment and operating costs (Kellens & Greyt, 2000; Zlich, 2000), so it is more and more widely used. However, no matter what kind of refining method, steaming method is used for deodorization. The above deodorized distillate usually contains: free fatty acid, glyceride, unsaponifiable

(unsaponifiable matter) (含植物化学成分，如角鲨烯、植物甾醇)和生育酚 (维生素 E) (Ramamurthi 等， 1996)。虽然其中物理精炼脱臭蒸馏物 (DODp)通常含有高浓度的游离脂肪酸 (70-85%), 但一般只是用于制备廉价肥皂或作动物饲料。 (unsaponifiable matter) (containing phytochemicals such as squalene, phytosterols) and tocopherols (vitamin E) (Ramamurthi et al., 1996). Although physically refined deodorized distillate (DODp) usually contains high concentrations of free fatty acids (70-85%), it is generally only used to make cheap soap or animal feed.

DODp与精炼油的产量比例是 2-3:100 (Frandsen, 1996)。近年来，全球及中国植物油年产量有稳定的增长，在 2005年分别达 1.2亿吨及 1400 万吨，因此，如能利用物理精炼脱臭蒸馏物来制备生物柴油将大幅降低其生产成本。发明内容 The ratio of DODp to refined oil production is 2-3:100 (Frandsen, 1996). In recent years, global and Chinese vegetable oil production has grown steadily, reaching 120 million tons and 14 million tons respectively in 2005. Therefore, the use of physical refining deodorized distillate to prepare biodiesel will significantly reduce its production costs. Summary of the invention

第一方面，本发明提供以植物油精炼副产物为原料制备生物柴油的方法。在用多种原料进行生物柴油的制备研究后，发明人意外地发现：在酸性和加热条件下，直接用甲醇与植物油精炼中副产的物理精炼脱臭蒸馏物反应，可制得高纯度和高收率的生物柴油。该方法相比现有技术工艺筒单、成本低廉。 In a first aspect, the present invention provides a method of preparing biodiesel from a vegetable oil refining by-product. After conducting research on the preparation of biodiesel with various raw materials, the inventors unexpectedly found that: under acidic and heated conditions, direct reaction with methanol and physical refining deodorized distillate by-product in vegetable oil refining can produce high purity and high purity. Yield of biodiesel. Compared with the prior art, the method is simple and low in cost.

在具体实施方案中，所述方法包括： In a specific embodiment, the method comprises:

a) 在酸性催化剂存在下使所述物理精炼脱臭蒸馏物与甲醇反应； b) 从反应混合物中分离脂肪酸曱酯。 a) reacting the physically refined deodorized distillate with methanol in the presence of an acidic catalyst; b) isolating the fatty acid oxime ester from the reaction mixture.

本发明所用酸催化剂可以是任何常规用于脂肪酸酯化的酸催化剂 , 包括但不限于质子酸如硫酸、硝酸、磷酸、硼酸和有机物磺酸，固体酸如强酸性阳离子交换树脂和沸石型催化剂，杂多酸如钨锗酸、磷钨酸、硅鵠酸、磷钼酸，以及某些盐如硫酸氢钠，优选为盾子酸，更优选为兼有脱水作用的浓硫酸。 The acid catalyst used in the present invention may be any acid catalyst conventionally used for fatty acid esterification, including but not limited to protic acids such as sulfuric acid, nitric acid, phosphoric acid, boric acid and organic sulfonic acids, solid acids such as strongly acidic cation exchange resins and zeolite-type catalysts. Heteropolyacids such as tungstic acid, phosphotungstic acid, silicic acid, phosphomolybdic acid, and certain salts such as sodium hydrogen sulfate, preferably turmeric acid, more preferably concentrated sulfuric acid having both dehydration effects.

在一优选实施方案中，所述物理精炼脱臭蒸馏物、曱醇和酸催化剂的摩尔比为 1 :9-11 :0.20，优选为 1 : 11 :0.20，但更多过量的甲醇对反应没有不利影响。 In a preferred embodiment, the molar ratio of the physical refining deodorized distillate, decyl alcohol and acid catalyst is 1:9-11:0.20, preferably 1:11:0.20, but more excess methanol does not adversely affect the reaction. .

本发明方法中，步骤 a)的反应温度优选为 65-85°C，更优选为约 75。C。反应时间优选为 15-60分钟，更优选为约 30分钟。 In the process of the present invention, the reaction temperature of the step a) is preferably from 65 to 85 ° C, more preferably about 75. C. The reaction time is preferably from 15 to 60 minutes, more preferably about 30 minutes.

步骤 a)酯化后的反应混合物中成分复杂，且物理化学性质相近，因此采用常规分离方法的收率和純度都不理想。在本发明的优选实施方案中，所述步骤 b)采用分子蒸馏法在约 140-145。C 的温度下进行。可选择地，所述分离可采用薄膜蒸发器在 160-170。C和 1毫米汞柱的减压条件下进行。 Step a) The composition of the reaction mixture after esterification is complex and has similar physicochemical properties, so the yield and purity of the conventional separation method are not satisfactory. In a preferred embodiment of the invention, step b) employs molecular distillation at about 140-145. Perform at the temperature of C. Alternatively, the separation may employ a thin film evaporator at 160-170. C and 1 mm Hg were carried out under reduced pressure.

第二方面，本发明提供处理植物油精炼中副产的物理精炼脱臭蒸馏物的方法，其包括如下步 In a second aspect, the present invention provides physical refining deodorization distillation for treating by-products in vegetable oil refining Method of matter, including the following steps

a) '在酸性催化剂存在下使所述物理精炼脱臭蒸馏物与曱醇反应； b) 从反应混合物中分离脂肪酸甲酯； a) 'reacting the physical refining deodorized distillate with decyl alcohol in the presence of an acidic catalyst; b) separating the fatty acid methyl ester from the reaction mixture;

c) 从残余物中提取植物甾醇。 c) Extracting plant sterols from the residue.

其中，步骤 a)和步骤 b)中所用的方法、试剂和反应条件如上述第一方面中所定义。 Wherein the methods, reagents and reaction conditions used in step a) and step b) are as defined in the first aspect above.

在本发明的优选实施方案中 , 步骤 c)通过将所述残余物加入极性有机溶剂中，并在低温下使所述植物醇结晶来进行。 In a preferred embodiment of the invention, step c) is carried out by adding the residue to a polar organic solvent and crystallizing the plant alcohol at low temperatures.

可用于本发明的极性有机溶剂包括但不限于醇、酮、醚、酯和卤代烃等，优选为醇、酮及其混合溶剂，更优选为甲醇和丙酮的混合溶剂。该混合溶剂中曱醇与丙酮的体积比优选为约 8:2。所述结晶过程的温度优选为不高于 -20°C, 更优选为约 -20。C，结晶时间优选为约 16-24小时。 The polar organic solvent usable in the present invention includes, but not limited to, an alcohol, a ketone, an ether, an ester, a halogenated hydrocarbon, etc., preferably an alcohol, a ketone, and a mixed solvent thereof, and more preferably a mixed solvent of methanol and acetone. The volume ratio of sterol to acetone in the mixed solvent is preferably about 8:2. The temperature of the crystallization process is preferably not higher than -20 ° C, more preferably about -20. C, the crystallization time is preferably about 16 to 24 hours.

在某些实施方案中，所述方法还包括从步骤 c)的植物甾醇结晶后的母液中提取维生素 E的步驟。 In certain embodiments, the method further comprises the step of extracting vitamin E from the mother liquor after crystallization of the plant sterol of step c).

第三方面，本发明提供处理植物油精炼中副产的物理精炼脱臭蒸馏物的方法，其包括如下步骤： In a third aspect, the present invention provides a method of treating a physically refined deodorized distillate by-product in vegetable oil refining, comprising the steps of:

a) 将游离脂肪酸从所述物理精炼脱臭蒸馏物中分离； a) separating free fatty acids from the physical refining deodorized distillate;

b) 从残余物中提取植物甾醇； b) extracting phytosterols from the residue;

c) 在酸性催化剂存在下使所述游离脂肪酸与甲醇反应，得到脂肪酸曱酯。 c) reacting the free fatty acid with methanol in the presence of an acidic catalyst to obtain a fatty acid oxime ester.

在一优选实施方案中，步骤 b)通过将所述残余物加入极性有机溶剂中，并在低温下使所述植物醇结晶来进行。其中，所述极性有机溶剂和结晶条件如上述第二方面所定义。 In a preferred embodiment, step b) is carried out by adding the residue to a polar organic solvent and crystallizing the plant alcohol at a low temperature. Wherein the polar organic solvent and crystallization conditions are as defined in the second aspect above.

步骤 c)中所用的酸催化剂可以是任何常规用于脂肪酸酯化的酸催化剂，包括但不限于质子酸如硫酸、硝酸、磷酸、硼酸和有机物磺酸，固体酸如强酸性阳离子交换树脂和沸石型催化剂，杂多酸如钨锗酸、磷钨酸、硅钨酸、磷钼酸，以及某些盐如 υ酸氢钠，优选为质子酸，更优选为兼有脱水作用的浓硫酸。 The acid catalyst used in step c) may be any acid catalyst conventionally used for fatty acid esterification, including but not limited to protic acids such as sulfuric acid, nitric acid, phosphoric acid, boric acid and organic sulfonic acids, solid acids such as strongly acidic cation exchange resins and The zeolite type catalyst, heteropoly acid such as tungstic acid, phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, and certain salts such as sodium hydrogen hydride, preferably a protic acid, more preferably concentrated sulfuric acid having a dehydrating action.

在本发明的优选实施方案中，所述脂肪酸、甲醇和酸催化剂的摩尔比为 1 :9-11 :0.20, 更优选为约 1 : 11 :0.20。 In a preferred embodiment of the invention, the molar ratio of the fatty acid, methanol and acid catalyst is from 1:9 to 1:0.20, more preferably from about 1:11:0.20.

优选地，步骤 c)在 65-85。C下进行，更优选在约 75。C进行。反应时间优选为 15-60分钟，更优选为约 30分钟。 Preferably, step c) is at 65-85. It is carried out under C, more preferably at about 75. C is carried out. The reaction time is preferably from 15 to 60 minutes, more preferably from about 30 minutes.

在一优选实施方案中，所述方法还包括从步驟 b)的植物醇结晶后的母液中提取维生素 E的步骤。 In a preferred embodiment, the method further comprises the step of extracting vitamin E from the mother liquor after crystallization of the plant alcohol of step b).

在某些实施方案中，步驟 a)进一步包括： 1) 将所述物理精炼脱臭蒸馏物与碱反应，使游离脂肪酸皂化；In certain embodiments, step a) further comprises: 1) reacting the physical refining deodorized distillate with a base to saponify the free fatty acid;

2) 从反应混合物中分离出皂化产物； 2) separating the saponified product from the reaction mixture;

3) 使所述皂化产物与酸反应，释放出脂肪酸。

限于氬氧纳、 -碳酸 i : 氬氧化钾和碳酸钾，更优选为氢氧化钾。 3) The saponified product is reacted with an acid to release a fatty acid.

It is limited to argon oxygen, - carbonic acid i: potassium argon oxide and potassium carbonate, and more preferably potassium hydroxide.

步骤 3)中所用的酸优选为质子酸，包括但不限于盐酸、硝酸、硫酸和磷酸等，更优选为 25%的硫酸。 The acid used in the step 3) is preferably a protic acid, including but not limited to hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, etc., more preferably 25% sulfuric acid.

在其它实施方案中，步骤 a)进一步包括： In other embodiments, step a) further comprises:

1) 65°C下将所述物理精炼脱臭蒸馏物与尿素的甲醇溶液混合； 1) mixing the physical refining deodorized distillate with a methanol solution of urea at 65 ° C;

2) 在 -20。C下静置，使反应混合物中析出尿素-脂肪酸复合物结晶；2) At -20. C is allowed to stand, and the urea-fatty acid complex crystals are precipitated in the reaction mixture;

3) 用 75%甲醇和己烷的混合溶液溶解所述尿素-脂肪酸复合物结晶；3) dissolving the urea-fatty acid complex crystal with a mixed solution of 75% methanol and hexane;

4) 分离上层有机层，除去己烷得到脂肪酸。 4) The upper organic layer is separated, and hexane is removed to obtain a fatty acid.

优选地，步骤 1)所用的尿素甲醇溶液中，尿素含量约为 0.33g/mL甲醇。步驟 3)的混合溶剂中 75%甲醇与己烷的体积比优选为 2: 1。 Preferably, the urea in methanol solution used in step 1) has a urea content of about 0.33 g/mL of methanol. The volume ratio of 75% methanol to hexane in the mixed solvent of the step 3) is preferably 2:1.

本发明方法适用于多种来源的植物油的精炼副产物，如向日葵籽、油菜籽、棉籽、棕榈、米糠、大豆、芥花籽和花生等，原料来源广泛，不受地域和季节的影响。 The method of the present invention is applicable to refinery by-products of vegetable oils from various sources, such as sunflower seeds, rapeseed, cottonseed, palm, rice bran, soybean, canola and peanuts, and has a wide range of raw materials, regardless of geographical and seasonal influences.

另外，本发明方法中各种过量的试剂，如甲醇、尿素、己烷和曱醇- 丙酮混合溶剂经过简单的分离和纯化步骤后均可循环使用。 Further, various excess reagents such as methanol, urea, hexane and decyl alcohol-acetone mixed solvents in the process of the present invention can be recycled after a simple separation and purification step.

本发明方法以植物油精炼中副产的物理精炼脱臭蒸馏物为原料，可制得高收率和高纯度的生物柴油和植物醇等产品，与现有技术相比成本大幅下降。 - 具体实施方式 The method of the present invention uses a physical refining and deodorizing distillate which is by-produced in vegetable oil refining as a raw material, and can obtain products of high yield and high purity such as biodiesel and phytol, which are significantly reduced in cost compared with the prior art. - detailed description

酯化反应 Esterification reaction

在酸催化剂作用下，使用过量的甲醇使物理精炼脱臭蒸馏物的游离脂肪酸转化为脂肪酸甲酯。剩余的甲醇可蒸馏回收再用，酸化废水可用碱中和，例如使用浓硫酸时用碳酸钾中和可产生 K₂SO₄肥料。结晶化植物甾醇 The free fatty acid of the physical refining deodorized distillate is converted to fatty acid methyl ester using an excess of methanol under the action of an acid catalyst. The remaining methanol can be distilled and reused, and the acidified wastewater can be neutralized with a base, for example, by neutralizing with potassium carbonate when concentrated sulfuric acid is used to produce K ₂ SO ₄ fertilizer. Crystallized phytosterol

植物醇在低温下不溶于极性溶剂，因此将物理精炼脱臭蒸馏物制备脂肪酸甲酯后的残余物与极性溶剂混合，在低温下静置，植物醇会结晶析出，通过过滤即可分离（Kircher & Rosenstein, 1973; Lin & Koseoglu, 2003; Pan等， 2005)。脱醇后的部分含有不同浓度的天然维生素 E及角鲨烯，可根据需要进行回收。皂化反应 The plant alcohol is insoluble in the polar solvent at a low temperature, so the residue obtained by preparing the fatty acid methyl ester in the physical refining deodorized distillate is mixed with the polar solvent, and is allowed to stand at a low temperature, and the plant alcohol crystallizes and can be separated by filtration ( Kircher & Rosenstein, 1973; Lin & Koseoglu, 2003; Pan et al., 2005). The alcoholic part contains different concentrations of natural vitamin E and shark Alkene can be recycled as needed. Saponification reaction

皂化反应指油脂在碱的作用下生成脂肪酸金属盐的反应，包括酯的水解和脂肪酸的中和。皂化反应常用的碱包括碱金属氢氧化物和碱金属碳酸盐，特别是 Na和 K的氢氧化物和碳酸盐。尿素 -脂肪酸复合 The saponification reaction refers to a reaction in which a fat or oil forms a fatty acid metal salt under the action of a base, including hydrolysis of an ester and neutralization of a fatty acid. Bases commonly used in the saponification reaction include alkali metal hydroxides and alkali metal carbonates, particularly hydroxides and carbonates of Na and K. Urea-fatty acid complex

尿素会与碳水化合物、脂肪酸、脂肪酸甲酯结合，形成不溶于水的结晶复合物 (Hayes等， 2000; 美国专利第 5,078,920号）。而环状化合物、芳香族化合物如植物翁醇等不会与尿素结晶。制备过程的监控 Urea combines with carbohydrates, fatty acids, and fatty acid methyl esters to form a water-insoluble crystalline complex (Hayes et al., 2000; U.S. Patent No. 5,078,920). On the other hand, cyclic compounds, aromatic compounds such as plant alcohols and the like do not crystallize with urea. Monitoring of the preparation process

本发明方法中，原料物理精炼脱臭蒸馏物含 70-90%的游离脂肪酸而显酸性，而产品脂肪酸甲酯不溶于水，因此在酯化过程中反应混合物的 pH值上升。利用 pH试剂可监测和实时估计酯化反应效率。 In the process of the present invention, the raw material physical refining deodorized distillate contains 70-90% of free fatty acid and is acidic, while the product fatty acid methyl ester is insoluble in water, so the pH of the reaction mixture rises during the esterification process. The efficiency of the esterification reaction can be monitored and estimated in real time using pH reagents.

此外，物理精炼脱臭蒸馏物在室温下是棕色固体，而本发明的脂肪酸甲酯是黄色澄清的液体，所以，透光度可作为反应进程的粗指针。 Further, the physical refining deodorized distillate is a brown solid at room temperature, and the fatty acid methyl ester of the present invention is a yellow clarified liquid, so that the transmittance can be used as a coarse indicator of the progress of the reaction.

也可采用常规滴定法 (如 ASTM D664)测定酸值 (acid no.)来计算酯化反应的效率及确定反应的终点。随机取样的样品可用气相质谱仪 (GC-MS) 进行分析，检验浓度和纯度。生物柴油中脂肪酸甲酯的含量通常要超过 98%以符合使用区域 (如：美国）的生物柴油标准。产品植物甾醇呈白色粉状结晶体，亦可采用气相质谱仪 (GC-MS)进行分析，测定产量和纯度。实施例 The acid value (acid no.) can also be determined by conventional titration (e.g., ASTM D664) to calculate the efficiency of the esterification reaction and determine the end point of the reaction. Randomly sampled samples can be analyzed by gas chromatography mass spectrometry (GC-MS) to verify concentration and purity. The content of fatty acid methyl esters in biodiesel is typically greater than 98% to meet biodiesel standards in the area of use (eg, US). The product phytosterol is a white powdery crystal which can also be analyzed by gas chromatography mass spectrometry (GC-MS) to determine the yield and purity. Example

以下将参照具体实施例对本发明的优选实施方案进行详细描述，但应当理解本发明并不限于这些具体的实施例。 The preferred embodiments of the present invention are described in detail below with reference to the specific embodiments, but it should be understood that the invention is not limited to these specific embodiments.

以下实施例中采用的物理精炼脱臭蒸馏物由合兴食用油精炼厂（地址：香港新界元朗唐人新村屏唐东街 9号合兴大厦)提供，由不同原料获得的脱臭蒸馏物的主要成分 (重量比)参见表 1。表 1 : 物理精炼脱臭蒸馏物的主要成 The physical refined deodorized distillate used in the following examples is supplied by Hexing Edible Oil Refinery (Address: Hexing Building, No. 9 Pingtang East Street, Tangren New Village, Yuen Long, New Territories, Hong Kong). The main components of deodorized distillate obtained from different raw materials. (weight ratio) see Table 1. Table 1: Main components of physical refining deodorized distillate

实施例 1

Example 1

将 130g曱醇、 7g浓^ ₎酸(98%)与 100g物理精炼脱臭蒸馏物 (花生，游离脂肪酸 85%, 甘油酯 10%, 植物甾醇 1.3%)混合，在摄氏 75度下反应 30分钟，溶液分层。分离得到下部液层，在进料速率 1毫升 /分钟，旋转片转速 10-20转 /分钟，蒸馏温度 140。C的条件下对所得反应混合物进行分子蒸馏，得到纯度 98.6%的脂肪酸曱酯，收率 86.1%。根据美国 ASTM D6751 的生物柴油检验方法，对所得脂肪酸曱酯的物理及化学特性进行检测，结果见表 2。 The alcohol 130g Yue, 7g concentrated _^) acid (98%) with 100g Physical refining deodorization distillate (peanuts, free fatty acids 85%, 10% glycerol, 1.3% phytosterols) were mixed, reacted at 75 ° C for 30 minutes The solution is layered. The lower liquid layer was separated at a feed rate of 1 ml/min, a rotating piece speed of 10-20 rpm, and a distillation temperature of 140. The obtained reaction mixture was subjected to molecular distillation under the conditions of C to obtain a fatty acid decyl ester having a purity of 98.6% in a yield of 86.1%. The physical and chemical properties of the obtained fatty acid oxime ester were tested according to the biodiesel test method of ASTM D6751. The results are shown in Table 2.

随后，将所得分子蒸馏残余物加入 350mL甲醇和丙酮的混合溶剂（8:2) 中，在摄氏零下 20度静置 24小时，析出植物甾醇结晶。随后过滤得到植物甾醇产品，收率达到 75% , 纯度 96%。实施例 2 Subsequently, the obtained molecular distillation residue was added to 350 mL of a mixed solvent of methanol and acetone (8:2), and allowed to stand at minus 20 ° C for 24 hours to precipitate phytosterol crystals. Subsequently, the plant sterol product was obtained by filtration, and the yield was 75% and the purity was 96%. Example 2

室温下，向 100g物理精炼脱臭蒸镏物 (芥花籽，游离脂肪酸 88%, 甘油酯 5.5%，植物甾醇 2.3%)中加入 10M的氢氧化钾 lOOmL和 200g甲醇，反应 10分钟。向反应混合物中加入 200mL己烷来萃取不皂化物两次。分离己烷层后，将肥皂液离心分层，得到上层肥皂层和下层水层。将肥皂层分离，加入 25%硫酸 34mL, 分离上层脂肪酸层。随后，加入 130g甲醇和 7g浓硫酸 (98%), 在 75。C反应 30分钟，得到上层脂肪酸甲酯层。分离得到纯度 99.6%的脂肪酸甲酯 87.9g，总收率 90%。 To 100 g of physical refining deodorized steamed food (canola seed, free fatty acid 88%, glyceryl ester 5.5%, phytosterol 2.3%), 10 M potassium hydroxide 100 mL and 200 g methanol were added at room temperature for 10 minutes. To the reaction mixture, 200 mL of hexane was added to extract the unsaponifiable matter twice. After separating the hexane layer, the soap liquid was centrifuged to obtain an upper soap layer and a lower aqueous layer. The soap layer was separated, and 34 mL of 25% sulfuric acid was added to separate the upper fatty acid layer. Subsequently, 130 g of methanol and 7 g of concentrated sulfuric acid (98%) were added at 75. C was reacted for 30 minutes to obtain an upper fatty acid methyl ester layer. The fatty acid methyl ester having a purity of 99.6% was isolated and found to be 87.9 g, and the total yield was 90%.

将己烷提取液在摄氏 45。C蒸馏，回收己烷，残留物加入 350mL甲醇和丙酮的混合溶剂（8:2)中，在摄氏零下 20度静置 24小时，分离沉淀的植物甾醇结晶，纯度 96% , 收率达到 77%。实施例 3 The hexane extract was at 45 °C. C distillation, recovery of hexane, the residue was added to 350 mL of a mixed solvent of methanol and acetone (8:2), and allowed to stand at minus 20 degrees Celsius for 24 hours to separate the precipitated phytosterol crystals with a purity of 96% and a yield of 77%. . Example 3

将 150g尿素溶于 450mL甲醇，然后注入 100g物理精炼脱臭蒸馏物 (大豆，游离脂肪酸 80%, 甘油酯 9.5%, 植物甾醇 1.8%)中，在摄氏 65 度下搅拌 30分钟。随后将反应混合物在 -20。C静置三小时，析出尿素-脂肪酸复合物结晶。过滤并用 200mL己烷洗涤结晶体。向滤液中注入 50mL 水，滤液分层。分离上层有机层并在摄氏 45。C蒸馏回收己烷，残留物加入 350mL甲醇和丙酮的混合溶剂（8:2)中，在 -20。C静置 24小时。分离沉淀的植物甾醇结晶，纯度达 95.5%, 收率 73%。 150 g of urea was dissolved in 450 mL of methanol, and then 100 g of physical refining deodorized distillate (soybean, free fatty acid 80%, glyceride 9.5%, phytosterol 1.8%) was poured and stirred at 65 ° C for 30 minutes. The reaction mixture was then brought to -20. C was allowed to stand for three hours to precipitate a crystal of the urea-fatty acid complex. The crystals were filtered and washed with 200 mL of hexane. 50 mL of water was poured into the filtrate, and the filtrate was layered. The upper organic layer was separated and was at 45 °C. The hexane was recovered by distillation, and the residue was added to 350 mL of a mixed solvent of methanol and acetone (8:2) at -20. C is allowed to stand for 24 hours. The precipitated phytosterol crystals were separated to a purity of 95.5% and a yield of 73%.

用 600mL 己烷和 75%甲醇混合液 (1 :2)溶解尿素-脂肪酸结晶，室温静置分层。下层为稀释的曱醇层，可蒸馏回收曱醇，同时尿素结晶沉淀。上层有机层在 40。C蒸熘回收己烷后，向残余物中加入 120mL甲醇和 5.6g 浓硫酸 (98%),于 75。C反应半小时。分离得到脂肪酸甲酯 74.8g，纯度 98%, 收率 77.2%。本发明脂肪酸甲酯产品各项指标与美国标准的对比 The urea-fatty acid crystals were dissolved in a mixture of 600 mL of hexane and 75% methanol (1:2), and the layers were allowed to stand at room temperature. The lower layer is a diluted sterol layer, which can be distilled to recover sterol, while the urea crystals precipitate. The upper organic layer is at 40. After distilling hexane from C, the residue was charged with 120 mL of methanol and 5.6 g of concentrated sulfuric acid (98%) at 75. C reacts for half an hour. The fatty acid methyl ester was isolated to give 74.8 g, purity 98%, yield 77.2%. Comparison of various indexes of fatty acid methyl ester products of the invention with American standards

表 2 的结果表明本发明由物理精炼脱臭蒸馏物制备的脂肪酸甲酯完全达到了美国生物柴油的标准。

The results in Table 2 indicate that the fatty acid methyl esters prepared by the physical refining deodorized distillates of the present invention fully meet the standards of the US biodiesel.

虽然以上具体描述了本发明某些优选实施方案和实施例，但本领域所属技术人员应当理解，在不脱离本发明基本精神和范围的前提下可对本发明实施方案进行各种修改和替换，而这些修改和替换均应包括在本发明的等同范围内。参考文献 Although certain preferred embodiments and examples of the invention have been described in detail above, the art It will be understood by those skilled in the art that various modifications and changes may be made to the embodiments of the present invention without departing from the spirit and scope of the invention. references

本文将所有涉及的文献如专利、期刊文章和教科书全文引入作参考。 All documents involved, such as patents, journal articles, and textbooks, are incorporated herein by reference.

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Claims

权利要求书 Claim

1. 以植物油精炼中副产的物理精炼脱臭蒸馏物为原料制备生物柴油的方法，包括： 1. A method for preparing biodiesel by using a physical refining deodorized distillate as a by-product in vegetable oil refining, comprising:

a) 65-85°C 和酸催化剂存在下使所述物理精炼脱臭蒸镏物与曱醇反应，产生脂肪酸甲酯； a) reacting the physically refined deodorized steamed product with sterol in the presence of an acid catalyst at 65-85 ° C to produce a fatty acid methyl ester;

b) 从反应混合物中分离所述脂肪酸曱酯。 b) separating the fatty acid oxime ester from the reaction mixture.

2. 如权利要求 1所述的方法，其中所述物理精炼脱臭蒸馏物、甲醇和酸催化剂的摩尔比为 1 :9-11 :0.20。 2. The method according to claim 1, wherein the physical refining deodorizing distillate, methanol and acid catalyst are in a molar ratio of 1:9-11:0.20.

3. 如权利要求 1或 2所述的方法，其中所述酸催化剂为浓硫酸。 3. Process according to claim 1 or 2, wherein the acid catalyst is concentrated sulfuric acid.

4. 如权利要求 1-3 中任一权利要求所述的方法，其中步骤 b)采用分子蒸馏法在 140-145。C的温度下进行。 4. A method according to any one of claims 1-3, wherein step b) employs a molecular distillation method at 140-145. The temperature of C is carried out.

5. 如权利要求 1-3 中任一权利要求所述的方法，其中步驟 b)采用薄膜蒸发器在 160-170。C和 1毫米汞柱的减压条件下进行。 5. A method according to any of claims 1-3, wherein step b) employs a film evaporator at 160-170. C and 1 mm Hg were carried out under reduced pressure.

6. 处理植物油精炼中副产的物理精炼脱臭蒸馏物的方法，包括： a) 在 65-85。C和酸催化剂存在下使所述物理精炼脱臭蒸馏物与曱醇反应； 6. A method of treating physical refining deodorized distillates by-products in vegetable oil refining, comprising: a) at 65-85. Reacting the physically refined deodorized distillate with decyl alcohol in the presence of C and an acid catalyst;

b) 从反应混合物中分离出脂肪酸曱酯； b) separating the fatty acid oxime ester from the reaction mixture;

c) 从所得残余物中提取植物甾醇。 c) extracting phytosterols from the resulting residue.

7. 如权利要求 6所述的方法，其中所述物理精炼脱臭蒸熘物、甲醇和酸催化剂的摩尔比为 1 :9-11 :0.20。 7. The method according to claim 6, wherein the physical refining deodorizer, methanol and acid catalyst have a molar ratio of 1:9-11:0.20.

8. 如权利要求 6或 7所述的方法，其中所述酸催化剂为浓硫酸。 8. The method of claim 6 or 7, wherein the acid catalyst is concentrated sulfuric acid.

9. 如权利要求 6-8中任一权利要求所述的方法，其中步骤 b)釆用分子蒸馏法在 140-145。C的温度下进行。 9. A method according to any one of claims 6-8, wherein step b) is by molecular distillation at 140-145. The temperature of C is carried out.

10. 如权利要求 6-8中任一权利要求所述的方法，其中步驟 b)采用薄膜蒸发器在 160-170。C和 1毫米汞柱的减压条件下进行。 10. A method according to any of claims 6-8, wherein step b) employs a thin film evaporator at 160-170. C and 1 mm Hg were carried out under reduced pressure.

11. 如权利要求 6-10中任一权利要求所述的方法，其中步骤 c)通过将所述残余物加入曱醇和丙酮的混合溶剂中，并在低温下使所述植物甾醇结晶来进行。 The method according to any one of claims 6 to 10, wherein the step c) is carried out by adding the residue to a mixed solvent of decyl alcohol and acetone, and crystallization of the plant sterol at a low temperature.

12. 如权利要求 11所述的方法，其中所述混合溶剂中甲醇和丙酮的体积比为 8:2。 The method according to claim 11, wherein a volume ratio of methanol to acetone in the mixed solvent is 8:2.

13. 如权利要求 11或 12所述的方法，其中所述结晶过程的温度不超过 -20^oC。 13. A method according to claim 11 or 12 wherein the temperature of the crystallization process does not exceed -20 ^o C.

14. 处理植物油精炼中副产的物理精炼脱臭蒸馏物的方法，包括： a) 分离所述物理精炼脱臭蒸馏物中的游离脂肪酸； 14. A method of treating a physically refined deodorized distillate by-product in vegetable oil refining, comprising: a) isolating free fatty acids in said physical refining deodorized distillate;

b) 从所得残余物中提取植物甾醇； b) extracting phytosterols from the resulting residue;

c) 在 65-85。C和酸催化剂存在下使所述脂肪酸与甲醇反应，产生脂肪酸甲酯。 c) at 65-85. The fatty acid is reacted with methanol in the presence of C and an acid catalyst to produce a fatty acid methyl ester.

15. 如权利要求 14所述的方法，其中步驟 b)通过将所述残余物加入甲醇和丙酮的混合溶剂中，并在低温下使所述植物甾醇结晶来进行。 The method according to claim 14, wherein the step b) is carried out by adding the residue to a mixed solvent of methanol and acetone, and crystallizing the phytosterol at a low temperature.

16. 如权利要求 15所述的方法，其中所述混合溶剂中甲醇和丙酮的体积、比为 8:2。 16. The method according to claim 15, wherein a volume ratio of methanol to acetone in the mixed solvent is 8:2.

17. 如权利要求 15或 16所述的方法，其中所述结晶过程的温度不超过 -20。C。 17. The method of claim 15 or 16, wherein the temperature of the crystallization process does not exceed -20. C.

18. 如权利要求 14-17中任一权利要求所述的方法，其中步骤 c)中所述脂肪酸、甲醇和酸催化剂的摩尔比为 1 :9-11 :0.20。 The method according to any one of claims 14-17, wherein the molar ratio of the fatty acid, methanol and acid catalyst in the step c) is 1:9-11:0.20.

19. 如权利要求 14-18中任一权利要求所述的方法，其中所述酸催化剂为浓 υ酸。 19. The method of any of claims 14-18, wherein the acid catalyst is concentrated citric acid.

20. 如权利要求 14-19中任一权利要求所述的方法，其中步骤 a)进一步包括： 20. A method according to any of claims 14-19, wherein step a) further comprises:

1) 使所述物理精炼脱臭蒸餾物与氢氧化钾反应 ,使游离脂肪酸皂化； 2) 从反应混合物中分离皂化产物； 1) reacting the physically refined deodorized distillate with potassium hydroxide to saponify the free fatty acid; 2) separating the saponified product from the reaction mixture;

3) 使所述皂化产物与 25%的硫酸反应，释放脂肪酸。 3) The saponified product is reacted with 25% sulfuric acid to release the fatty acid.

21. 如权利要求 14-19中任一权利要求所述的方法，其中步骤 a)进一步包括： 21. The method of any of claims 14-19, wherein step a) further comprises:

2) 在 -20°C下静置，使反应混合物中析出尿素-脂肪酸复合物结晶；2) standing at -20 ° C to precipitate a urea-fatty acid complex crystal in the reaction mixture;